CA2441826C - Pyridylmethylbenzamide and propamocarb derivative-based fungicide compositions - Google Patents

Abstract

The invention concerns fungicide compositions comprising: a) at least a pyridylmethylbenzamide derivative of formula (I) wherein the various radicals are such as defined in the description and b) at least a compound (II) which is propamocarb. The invention also concerns a curative or preventive method for fighting against phytopathogenic fungi of crops, characterised in that it consists in applying on the aerial parts of plants an efficient and non-phytotoxic amount of said fungicide compositions.

Description

FUNGICIDAL COMPOSITIONS BASED ON A DERIVATIVE
PYRIDYLMETHYLBENZAMIDE AND PROPAMOCARB

The present invention relates to novel fungicidal compositions comprising at least one pyridylmethylbenzamide derivative and propamocarb or one of its salts, compositions intended in particular for the protection of crops.
She also relates to a method for protecting crops against diseases fungal by application of these compositions.

[0002] It is known, in particular from the European patent application EP-A-1 056 723, pyridylmethylbenzamide compounds with a fungicidal action, making it possible to prevent the growth and development of phytopathogenic fungi that attack or are likely to attack crops.

On the other hand, propamocarb is a fungicidal active ingredient widely known and marketed, especially under the name Prévicur. Propamocarb, in the form of a salt with hydrochloric acid, is for example described in patents DE 1567169 and DE 1643040 and in "The Pesticide Manual", a World Compendium, 11th edition, CDS Tomlin, British Crop Protection Council, pages 1015-17, No. 599.

However, it is still desirable to improve the products usable by the farmer to fight against fungal diseases of crops, and especially 25 .. against mildew.

[0005] It is also always desirable to reduce the doses of products chemicals spread in the environment to combat attacks fungal crops, especially by reducing the application rates of the products.

It is finally still desirable to increase the number of products antifungals available to the farmer so that he finds them the better suited to its particular use.

ti

An object of the invention is therefore to provide a new composition fungicide, useful for solving the problems outlined above.

Another object of the invention is to propose a new composition.
fungicide useful in the preventive and curative treatment of diseases fungal example solanées, cereals and vines.

Another object of the invention is to propose a new composition fungicide with improved efficacy against mildew, oidiums, rust, botrytis of cereals, solanées and vine.

Another object of the invention is to propose a new composition fungicide with improved efficacy against downy mildew and / or powdery mildew and / or botrytis of the vine.

It has now been found that these goals could be achieved in whole or in partly thanks to the fungicidal compositions according to the present invention.

The present invention as broadly described hereinafter has therefore for firstly object fungicidal compositions comprising:
a) at least one pyridylmethylbenzamide derivative of formula (I):
(R3) q 4 lV

R1 (I) in which :
R 'is chosen from the hydrogen atom, an alkyl radical optionally substituted and an optionally substituted acyl radical;

2a R2 is selected from hydrogen and an alkyl radical optionally substituted;
= R3 and R4, identical or different, are independently selected from a halogen atom, the hydroxyl radical, the cyano radical, the nitro radical, The radical -SF5, the trialkylsilyl radical, an optionally substituted amino radical, a radical acyl, and a group E, OE or SE, wherein E is selected from a radical alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl and heterocyclyl, each of them being able to be possibly substituted;
= c represents 0, 1, 2, 3 or 4;
= q represents 0, 1, 2, 3 or 4;
as well as their possible optical and / or geometric isomers, tautomers and salts addition to an acid or a base acceptable in the field of agriculture;
and b) at least one compound (II) which is propamocarb.

In the definitions of the compounds of formula (1) set out above, the different radicals and chemical terms used have, unless specified contrary, following meanings:
"alkyl" or alkyl- "denotes a saturated hydrocarbon radical, linear or branched, containing 1 to 6 carbon atoms;
"alkenyl" denotes a hydrocarbon radical, linear or branched, containing of 1 to 6 carbon atoms and unsaturation as a double bond;
"alkynyl" denotes a hydrocarbon radical, linear or branched, containing of 20 = 1 to 6 carbon atoms and unsaturation as triple bond;
"alkoxy" means an alkyloxy radical;
"acyl" refers to the formyl radical or an alkoxycarbonyl radical;
"cycloalkyl" means a saturated cyclic hydrocarbon radical containing at 8 carbon atoms;
"aryl" means a phenyl or naphthyl radical;
"heterocyclyl" means a cyclic radical, unsaturated or totally or partially saturated, containing from 3 to 8 atoms, selected from carbon, nitrogen, sulfur and oxygen, for example and without limitation, pyridyl, pyridinyl, quinolyl, furyl, thienyl, pyrrolyl, oxazolinyl;
the term "possibly substituted" means that the so-called radicals may be substituted by one or more radicals selected from chlorine, bromine, fluorine, iodine, alkyl, alkoxy, hydroxy, nitro, amino; cyano and acyl.

The compounds of formula (I) are for example described in the application for EP-A-1,056,723 and, among these, the compounds possessing Moon the following features, singly or in combination:

= R 'and R2, identical or different, are independently selected from atom hydrogen and an optionally substituted alkyl radical;
R3 and R4, identical or different, are independently selected from halogen atom, hydroxy radical, nitro radical, amino radical s optionally substituted, an acyl radical, and a group E, OE or SE, in wherein E is selected from alkyl, cycloalkyl, phenyl and heterocyclyl, each of which can be optionally substituted;
= c represents 0, 1, 2 or 3;
= q represents 0, 1, 2 or 3;
s0 and their possible optical and / or geometric isomers, tautomers and salts addition to an acid or a base acceptable in the field of agriculture.

Among the compounds of formula (I), the compounds having the following characteristics, taken singly or in combination:
15 = R 'and R2, identical or different, are independently selected from atom hydrogen and a methyl or ethyl radical;
R3 and R4, identical or different, are independently selected from halogen atom, the nitro radical, an optionally substituted amino radical and one alkyl, cycloalkyl, phenyl or heterocyclyl radicals, each of which may to be Optionally substituted;
= c represents 1 or 2;
= q represents 1 or 2;
as well as their possible optical and / or geometric isomers, tautomers and salts addition to an acid or a base acceptable in the field of agriculture.

More particularly, the compounds of formula (1) possess the following characteristics:
R 1 and R 2 each represent the hydrogen atom;
R3 and R4, identical or different, are independently selected from 3o halogen atom, the nitro radical, an alkyl radical and the radical trifluoromethyl;
= c and q represent independently of each other 2;
as well as their possible tautomers and addition salts with an acid or a based, acceptable in the field of agriculture.

By way of example, the following compounds of formula (1) are all particularly preferred in the context of the present invention:

Compound (la): 2,6-dichloro-N - {[3-chloro-5- (trifluoromethyl) -2-pyridinyl]
methyl benzamide;
Compound (Ib): N - {[3-chloro-5- (trifluoromethyl) -2-pyridinyl] methyl} -2-fluoro 6-nitrobenzamide;
Compound (Ie): N - {[3-chloro-5- (trifluoromethyl) -2-pyridinyl] methyl} -2-methyl thyl-6-nitrobenzamide;
as well as their possible tautomers and addition salts with an acid or a based, acceptable in the field of agriculture.

It will be noted that in the invention as hereinafter claimed, the compound of formula (I) is exclusively the compound (la) described above and, the ratio compound (I) / compound (II) is selected to produce a synergistic effect.

The compound (II) defined above is propamocarb, i.e.
Propyl 3- (dimethylamino) propylcarbamate, described for example in "The Pesticide Manual ", 1st Edition, CDS Tomlin, British Crop Protection Council, pp. 1015-1017, No. 599. Advantageously, propamocarb used in the compositions according to the present invention will be in the form of hydrochloride, that is to say the addition salt of propamocarb with hydrochloric acid, known commercially under the name Prévicur.

Propamocarb, useful for the compositions according to the present invention.
invention, also be used in salt form with fosetyl, as described in request EP-A-1 056 755, or in the patent application WO-A-98/44801.

[0020] Advantageously, the compositions according to the present invention compound (Ia) or compound (Ib) or compound (Ic) with compound (II). Preferred compositions of the present invention include compound (Ta) with the compound (1I).

5a Thus, the present invention relates to fungicidal compositions comprising at least one pyridylmethylbenzamide derivative of formula (I), such than defined above and at least one compound (II) as defined above, the ratio (1) / compound (II) being between 1/500 and 1/1, of preference between 1/200 and 115, more preferably between 11150 and 1/10.

The compound (1) / compound (II) ratio is defined as being the ratio in weight of these 2 compounds. It is the same for any report of 2 compounds later in this text, to the extent that a different definition of this report is not expressly indicated.

It is understood that said fungicidal compositions can enclose a single compound (I) or more of such compound and / or one or more compounds (II) of such compound, as well as one or more other fungicidal compounds, herbicides, insecticides and / or plant growth regulators, depending on the use to which they are intended.

Thus the fungicidal compositions according to the present invention can also include, for example, one or more other active ingredients fungicides selected from acibenzolar-S-methyl, azoxystrobin, Benalaxyl, the benomyl, blasticidine-S, bromuconazole, captafol, captan, carbendazim, carboxin, carpropamide, chlorothalonil, fungicidal compositions based 1s. of copper, copper derivatives such as copper hydroxide and oxychloride copper, cyazofamid, cymoxanil, cyproconazole, cyprodinyl, dichloran, the diclocymet, diethofencarb, difenoconazole, diflumetorim, dimethomorph, diniconazole, discostrobin, dodemorph, dodine, edifenphos, epoxyconazole, ethaboxam, ethirimol, famoxadone, fenamidone, Fenarimol, fenbuconazole, fenhexamide, fenpiclonil, fenpropidine, the fenpropimorph, ferimzone, fluazinam, fludioxonil, flumetone, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, the folpel, the furalaxyl, furametpyr, guazatine, hexaconazole, hymexazol, imazalil, iprobenphos, iprodione, isoprothiolane, kasugamycin, kresoxim methyl, the Mancozeb, maneb, mefenoxam, mepanipyrim, metalaxyl and its forms enantiomers such as metalaxyl-M, metconazole, metiram-zinc, metominostrobin, oxadixyl, pefurazoate, penconazole, pencycuron, acid phosphorous and its derivatives such as fosetyl-Al, phthalide, picoxystrobin, the probenazole, prochloraz, procymidone, propiconazole, pyraclostrobin, the Pyrimethanil, pyroquilon, quinoxyfen, silthiofam, simeconazole, the spiroxamine, tebuconazole, tetraconazole, thiabendazole, thifluzamide, the thiophanate, for example thiophanate-methyl, thiram, triadimefon, triadimenol, tricyclazole, tridemorph, trifloxystrobin, triticonazole, the.
derived from valinamide such as, for example, iprovalicarb, vinclozoline, the Zineb and zoxamide.

Another object of the invention is a method of controlling, as a curative or preventive, against phytopathogenic fungi in crops, characterized in that one apply on the ground where grow or where are likely to grow plants, on leaves and / or fruits of plants or on plant seeds, a effective (agronomically effective) and non-phytotoxic amount of composition fungicide according to the invention.

The compositions according to the invention are advantageous for combating the fungal diseases of many crops, such as cereals, vegetables, solanées, vegetable crops, vines, fruits in general, and especially against mildew, ferns, septoria, Pythium sp. of these cultures.

The compositions according to the invention may also be used for fight against other phytopathogenic diseases of well-known cultures of a person skilled in the art who has at his disposal the compounds of formula (I) and the compounds (not)-[0028] These compositions generally improve significantly the actions respective and isolated compounds of the compound (I) and the compound (II) for a certain number of particularly harmful in crops, especially for solanées (tomatoes, potatoes, ...), especially for the mildew of the potato and tomato late blight, while maintaining an absence of phytotoxicity to these crops. It follows from this an improvement spectrum of activity and a possibility of decreasing the respective dose of each material active the latter quality being particularly important for reasons easily understood.

In the compositions according to the invention, the compound (I) / compound ratio (II) is advantageously chosen so as to produce a synergistic effect. We means by synergistic effect including that defined by Colby SR, in an article entitled "Calculation of synergistic and antagonistic responses of herbicidal combinations", Weeds, (1967), 15, pages. 20-22.

This last article uses the formula:
E = X + Y-XY

in which E represents the expected percentage of inhibition of the disease for the combination of both fungicides at defined doses (eg equal respectively at x and y), X is the observed percentage inhibition of the disease by compound (I) at a defined dose (equal to x), Y is the percentage inhibition observed of the disease by the compound (II) at a defined dose (equal to y).
When the observed inhibition percentage of the association is greater than E, there is effect 1o synergistic.

It is also understood by synergistic effect that defined by the application of the method of Tammes, "Isoboles, a graphie representation of synergism in Pesticides "
Netherlands Journal of Plant Pathology, 70 (1964), pp. 73-80.
The compound (I) / compound (II) report domains indicated above do not are in no way limiting the scope of the invention, but rather are cited in indicative, the person skilled in the art being quite able to carry out tests Additional to find other values of the dose ratio of these two compounds, for which a synergistic effect is observed.

[0033] Thus, the compositions according to the invention, comprising the compound (1) and the compound (II), allow to observe synergistic properties quite remarkable.
According to a variant of the compositions according to the invention, the ratio compound (I) / compound (II) is advantageously between 1/200 and 1/5, preferably between 1/140 and 1/10.

The invention thus also comprises the methods of treatment of the plants phytopathogenic diseases, characterized in that one applies a composition comprising at least one compound of formula (I) with at least one compound P. It is also possible to apply a composition containing both active substances, or else, either simultaneously or successively so as to to have the combined effect, two compositions each containing one of the two substances active.

These compositions cover not only compositions ready to to be applied to the crop to be treated by means of a suitable device, such as a device spraying, but also the concentrated commercial compositions which must be diluted before application to the crop.
The present invention provides a method of combating a large variety phytopathogenic diseases of crops, especially against septoria diseases and the mildews. The fight against these diseases can be achieved by application foliar direct.
The present invention thus provides a control method, as a curative or prevention, against phytopathogenic diseases of crops, which includes the treatment of the said culture (for example by application or by administration) with an effective and non-phytotoxic amount of an association as defined previously. By treatment of culture, we mean an application or administration of a fungicidal composition as described above on the aerial parts of the crops or on the soil where they grow and which are infested or likely to be infested by a phytopathogenic disease, such as mildew or Septoria, for example. By treatment of culture, we also mean the treatment of the reproductive products of the crop, such as seeds where the tubers for example.

The compositions described below are generally used for application to growing plants, or places where crops are grown, or to coating or lamination of seeds.

[0040] Among the appropriate means for applying the compositions according to the invention may be mentioned, the use of powders, sprays foliage, granules, mists or mousses, or in the form of suspensions of finely divided or encapsulated compositions; for soil treatments or some roots by liquid imbibitions, powders, granules, fumes or of the mosses; for application to plant seeds, use, as agents of coating or coating seeds, powders or liquid slurries.

.3s [0041] The compositions according to the invention are, as appropriate, applied to the vegetation and in particular to leaves infested with fungi plant pathogens. Another method of applying the compounds or compositions according to the invention is the addition of a formulation containing the Contents active, to irrigation water. This irrigation can be an irrigation at way sprinklers.

Formulations suitable for the applications of the compositions according to the invention include formulations suitable for use under form of, for example, sprays, powders, granules, mists, foams, emulsions or other.
In practice, for the fight against phytopathogenic diseases of crops, one method, for example, is to apply to plants or middle in which they push an effective amount of a composition according to the invention.
For such a method, the active ingredients are generally applied to the place even where the infestation must be controlled, and at a dose of effectiveness between about 1 g and about 1000 g of active ingredients, in total, per hectare of treated place.
Under ideal conditions, depending on the nature of the phytopathogenic fungus at treat a lower dose may provide adequate protection. Conversely, bad weather conditions, resistance or other factors may require doses higher active ingredient.

Effective use doses of the associations employed in the invention may vary in large proportions, in particular depending on the nature of the phytopathogenic fungi to eliminate or the degree of infestation, for example, of the plants by these mushrooms.

The optimum dose usually depends on several factors, for example example the type of phytopathogenic fungus to be treated, the type or level of development of the infested plant, the density of vegetation, or the method of application. More preferably, an effective dose of materials active (I) and (II) is from about 5 g / ha to about 700 g / ha.

For their use in practice, the compositions according to the invention can be used alone and can also be advantageously used in Formulations containing one or other of the active ingredients or both 'sets, in combination or association with one or more other components compatible which are for example solid fillers or diluents or liquids, adjuvants, surfactants, or the like, suitable for use desired and which are acceptable for use in agriculture. The formulations can be any type known in the field and suitable for application in all types of s plantations or crops. These formulations that can be prepared from all known manner in this field, are likewise part of the invention.

[0047] The formulations may also contain other types of ingredients such as protective colloids, adhesives, thickeners, agents thixotropic penetrating agents, spraying oils, stabilizers, conservatives (in particular anti-mold agents), sequestering agents, or others, as well as other known active ingredients with pesticidal properties (in particular particular fungicides, insecticides, acaricides, nematicides) or with properties of plant growth regulator. More generally, the compounds used in The invention may be combined with any solid or liquid additives corresponding to the usual formulation techniques.

In general, the formulations according to the invention contain habitually from about 0.05% to about 99% (by weight) of one or more compositions according to 20- the invention, from about 1% to about 95% of one or more solid charges or liquids, and possibly from about 0.1% to about 50% of one or more other compatible compounds, such as surfactants or the like.

In the present description, the term "charge" means a component organic or Inorganic, natural or synthetic, with which the active components are combined to facilitate its application, for example, to plants, seeds, or ground.
This charge is therefore generally inert and must be acceptable ( example acceptable for agronomic purposes, in particular for treating the plants).
The filler may be solid, for example, clays, natural silicates or synthetic materials, silica, resins, waxes, solid fertilizers (eg salts ammonium), natural minerals from the soil, such as kaolins, clays, talc, lime, quartz, attapulgite, montmorillonite, bentonite or diatomaceous earth, or minerals 3s synthetic, such as silica, alumina, or silicates, in particular aluminum silicates or magnesium. The solid charges suitable for the granules are the natural rocks, crushed or crushed, such as calcite, marble stone pumice, sepiolite, and dolomite; synthetic granules of inorganic flours or organic; granules of organic material such as sawdust, walnut bark coconut, ear or shell of corn or tobacco stalk; kieselguhr, tricalcium phosphate, cork powder, or carbon black adsorbent; soluble polymers in water, resins, waxes;
or solid fertilizers. Such compositions can, if desired, contain one or several compatible agents such as wetting agents, dispersants, emulsifiers or dyes which when solid can also serve as diluents.

The fillers can also be liquid, for example: water, alcohols, in particular butanol or glycol, as well as their ethers or esters, in particular acetate methylglycol; ketones, in particular acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone or isophorone; oil cuts such as hydrocarbons parafinic or aromatic, in particular xylenes or alkylnaphthalenes;
oils mineral or vegetable; chlorinated aliphatic hydrocarbons, in particular trichloroethane or methylene chloride; chlorinated aromatic hydrocarbons, in especially chlorobenzenes; solvents soluble in water or strongly polar dimethylformamide, dimethylsulfoxide, N, N-dimethylacetamide, N-methylpyrrolidone; N-octylpyrrolidone, liquefied gases; or others, be taken separately or in mixture.

The surfactant may be an emulsifying agent, an agent dispersant, or wetting agent, of ionic or nonionic type or a mixture of these agents surfactants. Among these, for example, acid salts are used.
polyacrylic, 25 = lignosulfonic acid salts, phenolsulfonic acid salts or naphthalenesulphonic, polycondensates of ethylene oxide with alcohols fat or fatty acids or fatty esters or fatty amines, phenols substituted (especially alkylphenols or arylphenols), ester-salts of acid sulfosuccinic acid, taurine derivatives (in particular alkyltaurates), esters phosphoric alcohols or polycondensates of ethylene oxide with phenols, esters of fatty acids with polyols, or functional derivatives sulphates, sulfonates or phosphates of the compounds described above. The presence of minus one surfactant is usually essential when active ingredients and / or inert filler are only sparingly soluble or insoluble in water and when the charge of said composition to be applied is water.

The formulations according to the invention may further contain other additives such as adhesives or dyes. Adhesives such as carboxymethyl cellulose, or synthetic or natural polymers in the form of powders, granules or matrices, such as gum arabic, latex, polyvinylpyrrolidone, alcohol polyvinyl or polyvinyl acetate, natural phospholipids, such as cephalins or lecithins, or synthetic phospholipids may be used in the formulations. It is possible to use dyes such as pigments inorganic, such as for example: iron oxides, titanium oxides, or blue of Prussia; organic coloring matters, such as those of the alizarin type, azo, .to or metal phthalocyanines; or trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum or zinc.

The formulations containing the compositions of the invention, which are used to control phytopathogenic fungi in crops, can also contain stabilizers, other fungicides, insecticides, miticides, nematicides, anti-helminths or anti-coccidoses, bactericides, agents attractants or repellents or pheromones for arthropods or vertebrates, deodorants, flavors, or dyes.

These can be chosen on purpose to improve the power, the persistence, safety, spectrum of action on fungi phytopathogenic cultures or to make the composition capable of performing other functions helpful for treated surfaces.

For their use in agriculture, the compositions according to the invention, are by therefore formulated in various solid or liquid forms.

As solid formulations, mention may be made of dusting powders (for example active ingredient content up to 100%) and granules, especially those obtained by extrusion, atomization, compacting, impregnation of a support granulation, granulation from a powder (the content of active ingredients in these granules being between 0.5 and 80% for the latter cases).

The fungicidal compositions according to the invention can still be used under powder form for dusting; we can also use formulations comprising 50 g of active ingredients and 950 g of talc; we can also use formulations comprising 20 g of active material, 10 g of finely divided silica and 970 g talcum powder; we mix and grind these constituents and apply the mixture by dusting.
As liquid formulations or intended to constitute compositions during the application, solutions can be mentioned, in particular concentrates soluble in water, emulsifiable concentrates, emulsions, suspensions concentrated, wettable powders (or powder spray).

The concentrated suspensions, applicable in spraying, are prepared from in order to obtain a stable fluid product that does not deposit and leads to a good bio-availability of active ingredients. These suspensions contain usually from 5% to 75% of active ingredients, preferably from 10% to 25%
%, of 0.5 to 75% of surfactants, preferably 5% to 50%, from 0 to 10%
additives suitable as thickeners of organic or mineral origin, of the anti-foaming agents, corrosion inhibitors, adhesives, preservatives, such as Proxel GXL, antifreezes and, as a carrier, water or a organic liquid in which the active ingredients are little or not soluble:
some organic solids or mineral salts may be dissolved in the support to help prevent sedimentation or as antifreeze for water.
In certain cases, and in particular for formulations intended for the treatment of seeds, one or more dyes may be added.

For foliar applications, the choice of surfactants is important for ensure good bio availability of active ingredients; so, we will use of preferably a combination of a hydrophilic surfactant (HLB> 10) and of a lipophilic surfactant (HLB <5).

By way of example, here are 3 possible formulations of the suspension type concentrated, adapted to different cultures:

Example SC 1 (in g / kg):
This example is rather suitable for monocotyledonous crops (cereals, rice,......) - active ingredients 150 *
surfactant of hydrophilic nature (for example Rhodasurf 860P) 300 lipophilic surfactant (for example Plurafac LF 700) 150 * (trademarks) - ethoxylated tristyrylphenol phosphate 50 - Antifoam 5 propylene glycol 30 -? rosi1200 * 20 - ttagel 50 * 40 - water (qs 1 kg) 255 Example SC2 (in g / kg) This example is rather adapted to dicotyledonous crops (vine, tree Orchard ......) - active ingredients 150 Hydrophilic surfactant (for example Rhodasurf 860P) 150 - ethoxylated tristyrylphenol phosphate 50 - Antifoam 5 propylene glycol 30 - perosil 200 * 20 - Pttage150 * 40 - water (qs 1 kg) 555 Example SC3 (in g / kg) This example is more specifically adapted to seed treatment.
- active ingredients 50 surfactant of hydrophilic nature (for example Rhodasurf 860P) ethoxylated tristyrylphenol phosphate 15 - antifoam 1 propylene glycol 30 - dye 20 -Rhodopol G * 1,5 -P roxel GXL * 1.5 - water (qs 1 kg) 876 To achieve these formulations, the procedure will preferably be used next :
* (trademarks) To the required quantity of water, by means of a turbine stirrer, one mixes the selected surfactants (hydrophilic surfactant + surfactant character lipophilic + ethoxylated tristylphenol phosphate); after homogenization, mixed then the other constituents of the formula apart from the active ingredients.

The active ingredients and optionally the thickener are then added original mineral (aerosil 200 and attagel 50) to obtain a medium of consistency viscous.
The resulting mixture is then milled using a large grinding turbine.
speed then a ball mill until a D50 of the order of 1 to 3 m and a D90 between 3 and 8 m.

In the case where no thickener of mineral origin has been used, then add the thickener of natural origin (Rhodopol G) and shake until a adequate viscosity.

Wettable powders (or spray powder) are usually prepared in such a way that they contain from 20% to 95% of active, and they usually contain, in addition to the solid support, from 0% to 30%
an agent wetting agent, from 3% to 20% of a dispersing agent, and, when necessary, 0.1% to 10% of one or more stabilizers and / or other additives, such as penetration, adhesives, or anti-caking agents, dyes, etc.

To obtain the powders to be sprayed or wettable powders, one mixed intimately the active ingredients in the appropriate mixers with the substances additional and milled with mills or other suitable grinders. We gets powders whose wettability and suspension are advantageous; they can be suspended with water at any concentration desired and these suspensions can be used very advantageously in particular for the application for example on the leaves of the plants or on the seeds.

By way of example, here are various compositions of wettable powders (or powders to be sprayed):

* (trademark) 16a Example PM 1 - active ingredients 50%
- ethoxylated fatty alcohol (wetting agent) 2.5%
- ethoxylated phenylethylphenol (dispersing agent) 5%
- chalk (inert support) 42.5%
Example PM 2:
- active ingredients 10%

- oxo synthetic alcohol of branched type, C 13 ethoxylated with 8 to 10 oxide ethylene (wetting agent) 0.75%
- neutral calcium lignosulfonate (dispersing agent) 12%
- calcium carbonate (inert filler) qs 100%
Example PM 3:
This wettable powder contains the same ingredients as in the example preceding, in the following proportions:
- active ingredients 75%
Yo - wetting agent 1,50%
- dispersing agent% 8%
- calcium carbonate (inert filler) qs 100%
Example PM 4:
ss. - active ingredients 90%
- ethoxylated fatty alcohol (wetting agent) 4%
- ethoxylated phenylethylphenol (dispersing agent) 6%
Example PM 5:
20 - active ingredients 50%
- mixture of anionic and nonionic surfactants (wetting agent) 2.5%
- sodium lignosulfonate (dispersing agent) 5%
- kaolinic clay (inert support) 42.5%

[00661 Dispersions and aqueous emulsions, for example compositions obtained by diluting with water a wettable powder according to the invention, are included in the general scope of the present invention. Emulsions can be of the water-in-oil or oil-in-water type and they may have a consistency thick like that of a "mayonnaise".
The fungicidal compositions according to the invention can be formulated under the form of dispersible granules in water also included in the scope of the invention. These dispersible granules, of apparent density generally range between about 0.3 and 0.6 have a particle size generally comprised of enter about 150 and 2000 and preferably between 300 and 1500 microns.

The active ingredient content of these granules is generally included enter about 1% and 90%, and preferably between 25% and 90%. The rest of the pellet is essentially composed of a solid filler and possibly adjuvants surfactants active agents imparting to the granule dispersibility properties in water. These granules s can be essentially of two different types depending on whether the load restraint is soluble or not in water. When the charge is water soluble, it can be mineral or, preferably, organic. Excellent results have been obtained with urea.
In the In the case of an insoluble filler, it is preferably mineral, as example the kaolin or bentonite. It is then advantageously accompanied by agents surfactants so-called active ingredients (2 to 20% by weight of the granules) of which more than half is, by example, consisting of at least one dispersing agent, essentially anionic, such alkali earth or alkaline earth polynaphthalene sulphonate or lignosulfonate alkaline or alkaline-earthy, the rest being non-wetting agents ionic or anionic compounds such as an alkaline or alkaline earth metal naphthalene sulphonate.
By In addition, although this is not essential, we can add admixtures such as anti-foam agents.

The granule can be prepared by mixing the necessary ingredients then granulation according to several techniques known per se (bezel, fluid bed, atomizer, Extrusion, etc ...). It usually ends with crushing followed by sieving at the particle size chosen within the limits mentioned above. We can still use granules obtained as before and then impregnated with a composition containing the active ingredients.

[0070] Preferably, it is obtained by extrusion, operating as indicated in the examples below.
Example GD1: Dispersible granules In a mixer, 90% by weight of the active ingredients are mixed with 10%
urea pearls. The mixture is then milled in a pin mill. We get a Powder which is moistened with about 8% by weight of water. The wet powder is extruded in a perforated roll extruder. A granulate is obtained which is dried, then crushed and sieved, so as to keep only the granules respectively a dimension between 150 and 2000 microns.

EXAMPLE GD2 Dispersible Granules In a mixer, the following constituents are mixed:

- active ingredients 75%
- wetting agent (sodium alkylnaphthalene sulphonate) 2%
- dispersing agent (sodium polynaphthalene sulphonate) 8%
- inert load insoluble in water (kaolin) 15%
This mixture is granulated in a fluid bed, in the presence of water, and then dried, crushed and sieved to obtain granules of size between 0.15 and 0.80 mm.

These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used for prepare compositions with other active ingredients, in particular fungicides, these the last being in the form of wettable powders, or granules or suspensions aqueous.
The fungicidal compositions according to the invention contain usually from 0.5 to 95% of the combination of the compound (I) and the compound (II). It could be of the concentrated composition, that is to say the commercial product combining the compound (I) and the compound (II). It can also be the diluted composition ready to to be applied to the cultures to be treated. In the latter case dilution with water may be made from a commercial concentrate composition containing the compound (I) and the compound (II) (this mixture is called "ready-to-use" or again ready mix, in English), or by means of extemporaneous mixing (called in English "tank mix") of two concentrated commercial compositions containing each the compound (I) and the compound (II).

The invention finally relates to a method of fighting, as a curative or preventive, against phytopathogenic fungi in crops, characterized in that one applies to plants to treat an effective amount and not phytotoxic a fungicidal composition according to the invention.

Phytopathogenic fungi from cultures that can be combated by this process are especially those:

- from the group of oomycetes:
- of the genus Phytophthora such as Phytophthora infestans (downy mildew) solanées, especially potatoes or tomatoes), - of the Peronosporaceae family, in particular Plasmopara viticola (late blight) vine), Plasmopara halstedii (sunflower mildew), Pseudoperonospora sp (including late blight of cucurbitaceae and hops), Bremia lactucae (downy mildew of 5 lettuce), Peronospora tabacinae (tobacco blight), Peronospora parasitica (Cabbage mildew), Peronospora viciae (pea mildew), Peronospora destructor (onion mildew);

- of the group of adelomycetes:
10 - of the genus Alternaria, for example Alternaria solani (alternaria of solanées, including tomatoes and potatoes), - of the genus Guignardia, in particular Guignardia bidwelli (black rot of the vine), - of the genus Oidium, for example powdery mildew of the vine (Uncinula necator), powdery mildew in vegetable crops, eg Erysiphe polygoni (powdery mildew) cruciferous), Leveillula taurica, Erysiphe cichoracearum, Sphaerotheca fuligena, (cucurbitaceous powdery mildew, compound, tomato), Erysiphe communis (powdery mildew beet and cabbage), Erysiphe pisi (pea powdery mildew) alfalfa), Erysiphe polyphaga (bean and cucumber powdery mildew), Erysiphe umbelliferarum (Umbelliferum powdery mildew, especially carrot), Sphaerotheca humuli (powdery mildew hops);

- of the group of soil fungi:
- of the genus Pythium sp., - of the genus Aphanomyces sp., in particular Aphanomyces euteiches (rot pea), Aphanomyces cochlioides (black beet rot).

By the expression "applied to the plants to be treated", we mean mean, at meaning of the present text, that the fungicidal compositions of the invention can be applied by means of different treatment processes such as:
- Spraying on the aerial parts of said plants with a liquid comprising one of said compositions, - dusting, incorporation into the soil of granules or powders, watering, around the so-called plants, and in the case of trees the injection or the painting, coating or lamination the seeds of said plants with a porridge

21 comprising one of said compositions.

Spraying a liquid on the aerial parts of crops to treat is the preferred method of treatment.
The following examples are given purely for illustrative purposes.
the invention and do not limit it in any way.

Although the invention has been described in terms of many variants preferred, those skilled in the art will appreciate that many modifications, substitutions, omissions and changes can be made without departing from the mind of it. Thus, it is understood that the scope of the present invention is limited only by the scope of the following claims, as well as by their equivalents.
Example: Testing a composition against potato late blight (Phytophthora infestans: preventive action1 The following active ingredients are used for this test:
- Compound (Ia) as a concentrated suspension (10 SC) - Compound (II): propamocarb hydrochloride (Prévicur-N, in the form of soluble concentrate (66.5 SL).

Potato plants (three weeks old) are treated with spray automatic (Mardrive) at the rate of 200 1 / ha. Six identical tests are performed. The compounds (Ia) and (II) are mixed ("tank-mix") in different proportions expressed in the table of results in g / ha.

All plants are inoculated 24 hours after treatment with a suspension of sporangia of Phvtonhthora infestans at 20,000 spores per ml.

The inoculated plants are covered for 2 days then put under an atmosphere controlled at 20 C until reading the results.
The degree of infestation is assessed by rating on a scale from 1 to 10, the value 0 denoting absence of disease, value 100 denoting an infestation Total 35. (100%). .

22 For each treatment, the percentage of control of the disease is calculated by compared to untreated plants, and the theoretical results are calculated thanks to the Colby formula previously described.
The difference between the experimental results and the calculated results allows determine the degree of synergy between the two compounds.

The results are presented in the following table:

Compound test (la and compound (1D:
Concentration (g / ha) Rating Efficiency% Synergy (Colby) Compound (la) 5 4.3 48 -25 3.3 60 -Compound (I) 400 8.3 0 -600 6.8 18 -(la) + (II) 1/80 5 + 400 2.8 66 18 (Ia) + (11) 1/120 5 + 600 2.2 74 17 (la) + (II) 1/16 25 + 400 1.5 82 22 (la) + (11) 1/24 25 + 600 1.0 88 21 Untreated control: Rating 8.3 The compositions according to the invention comprising the compound (Ia) and the compound (II) have a strong synergy, regardless of the doses of each of the Contents active and regardless of the proportions compound (la) / compound (II).

Claims (11)

1. Fungicidal composition comprising:

a) a compound (I) chosen from 2,6-dichloro-N - {[3-chloro-5-(Trifluoromethyl) -2 pyridinyl] methyl} benzamide, its possible optical Isomers and / or geometric, tautomers and its addition salts with an acid or a base acceptable in the field of agriculture; and b) a compound (II) which is propamocarb, the compound (I) / compound (II) ratio being selected so as to produce a effect synergistic. 2. Synergistic fungicidal composition according to claim 1, characterized in that this that the ratio compound (I) / compound (II) is between 1/200 and 1/5. 3. Synergistic fungicidal composition according to claim 2, characterized in that this that the ratio compound (I) / compound (II) is between 1/140 and 1/10. 4. Fungicidal composition according to any one of claims 1 to 3, characterized in that it comprises in addition to the compounds (I) and (II) a support inert suitable in agriculture and possibly a suitable surfactant in Agriculture. 5. Fungicidal composition according to any one of claims 1 to 4, characterized in that it comprises from 0.5 to 99% of the combination of the compound (I) and compound (II). 6. Control method, whether curative or preventive, against fungi phytopathogenic crops, characterized in that it is applied to the soil or grow or where are likely to grow the plants, on the leaves and / or fruits of plants or on plant seeds, a quantity agronomically effective and non-phytotoxic of a fungicidal composition according to any of claims 1 to 5. 7. Method according to claim 6, characterized in that the composition fungicide is applied by spraying a liquid on the parts aerial crops to be treated. 8. Process according to claim 6 or 7, characterized in that the quantity of fungicidal composition corresponds to a dose of compound (I) and compound (II) between 1 g / ha and 1000 g / ha. 9. Process according to any one of claims 6 to 8, characterized in that that the treated crop is tomato, potato or vine. 10. Process according to claim 9, characterized in that the fungus plant pathogen is the late blight of tomato, potato and the vine. 11. Product comprising a compound (I) and a compound (II) as defined in the claim 1 as a combined preparation for simultaneous use, separate or sequential in the fight against phytopathogenic fungi of the in one place, the compound (1) / compound (II) ratio being selected from way to produce a synergistic effect.